Catalysis design: from Ti-bis(enolato-imino) to Ti-bis(enolato-azo) in living olefin polymerization at DFT level
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- 作者：Gaetano Giammarino ; Vincenzo Villani
- 关键词：DFT calculation ; Reaction mechanisms ; H ; transfer termination ; Fluorine interactions ; Post ; metallocene catalysis ; Living polymerization
- 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
- 出版年：2016
- 出版时间：March 2016
- 年：2016
- 卷：135
- 期：3
- 全文大小：824 KB
- 参考文献：1.Matsui S, Mitani M, Saito J, Tohi Y, Makio H, Matsukawa N, Takagi Y, Tsuru K, Nitabaru M, Nakano T, Tanaka H, Kashiwa N, Fujita T (2001) J Am Chem Soc 123:6847–6856CrossRef
2.Terao H, Iwashita A, Matsukawa N, Ishii S, Mitani M, Tanaka H, Nakano T, Fujita T (2011) ACS Catal 1:254–265CrossRef
3.Milano G, Cavallo L, Guerra G (2002) J Am Chem Soc 124:13368–13369CrossRef
4.Yu S-M, Mecking S (2008) J Am Chem Soc 130:13204–13205CrossRef
5.Bryliakov KP, Talsi EP, Möller HM, Baier MC, Mecking S (2010) Organometallics 29:4428–4430CrossRef
6.Möller HM, Baier MC, Mecking S, Talsi EP, Bryliakov KP (2012) Chem Eur J 18:848–856CrossRef
7.Guironnet D, Caporaso L, Neuwald B, Goetker-Schnetmann I, Cavallo L, Mecking S (2011) J Am Chem Soc 133:2329CrossRef
8.Tanaka R, Viehmann P, Hecht S (2012) Organometallics 31:4216–4220CrossRef
9.Giammarino G, Villani V (2014) Macromol Theory Simul 23:365CrossRef
10.Villani V, Giammarino G (2010) Macromolecules 43:5917–5918CrossRef
11.Gaussian 09 (2009) Revision A.02. Gaussian, Inc., Wallingford CT
12.Cossi M, Rega N, Scalmani G, Barone V (2003) J Comput Chem 24:669–681CrossRef - 作者单位：Gaetano Giammarino (1)
Vincenzo Villani (1)
1. Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell’Ateneo Lucano 10, 85100, Potenza, Italy - 刊物类别：Chemistry and Materials Science
- 刊物主题：Chemistry
Theoretical and Computational Chemistry
Inorganic Chemistry
Organic Chemistry
Physical Chemistry - 出版者：Springer Berlin / Heidelberg
- ISSN：1432-2234
文摘
Reaction mechanisms of both propagation and termination steps in homogeneous polyolefin catalysis are investigated at DFT level. Starting from existent catalysts, we propose the design of a new Ti-bis(enolato-azo) catalytic family. We considered a number of hydrogenated or fluorinated models in aromatic group and chelating ring. Fluorination in the aromatic rings is able to control the propagation steps by activating the metal site, while hydrogenation of the ligand can inhibit the termination transfers. So, we have optimized the structure of the catalyst to give it the highest reactivity towards polymerization and the lowest one towards termination, by means of the meta-F substitutions in the aromatic group, and –CH2CF3 on the chelating ring. Thus, the developed bis(enolato-azo) models seem to be interesting for experimental investigations as new living catalysts. Keywords DFT calculation Reaction mechanisms H-transfer termination Fluorine interactions Post-metallocene catalysis Living polymerization